Dibasic esters and the use thereof in plasticizer compositions

ABSTRACT

Dibasic esters (diesters) and their use in plasticizer compositions are generally disclosed. In some embodiments, the diesters are branched-chain esters of long-chain alkanedioic acids, such as octadecanedioic acid. In some embodiments, such plasticizer compositions are used to increase the plasticity of a polymer resin, such as a vinyl chloride resin or poly vinyl butyral. In some other embodiments, such plasticizer compositions are used to lower the glass transition temperature of a polymer resin. In some embodiments, at least a portion of the plasticizer is derived from a renewable source, such as a natural oil.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority of U.S.Provisional Application Nos. 61/954,378, filed Mar. 17, 2014; and62/048,382, filed Sep. 10, 2014. The aforementioned priorityapplications are hereby incorporated by reference as though fully setforth herein in their entirety.

TECHNICAL FIELD

Dibasic esters (diesters) and their use in plasticizer compositions aregenerally disclosed. In some embodiments, the diesters arebranched-chain esters of long-chain alkanedioic acids, such asoctadecanedioic acid. In some embodiments, such plasticizer compositionsare used to increase the plasticity of a polymer resin, such as a vinylchloride resin or poly vinyl butyral. In some other embodiments, suchplasticizer compositions are used to lower the glass transitiontemperature of a polymer resin. In some embodiments, at least a portionof the plasticizer is derived from a renewable source, such as a naturaloil.

BACKGROUND

It can often be desirable to modify the properties of a polymer resinthrough the addition of certain additives. Plasticizers are one suchclass of additives that can be added to a polymer resin to changecertain properties of the resulting composition. These changes inproperties include lowering the glass transition temperature of theresin, increasing the plasticity (e.g., flowability) of the resin, andthe like.

Inclusion of plasticizers into polymer compositions is not without itsproblems, however. For example, plasticizer compounds can often migratewithin the composition and migrate to the surface or to boundaries(e.g., boundaries in a laminate). Therefore, there is a continuing needto develop new plasticizer compounds and compositions, where theplasticizer compounds are less susceptible to migration within thepolymer.

SUMMARY

In a first aspect, the disclosure provides compounds of formula (I):

wherein: X¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene, each of which isoptionally substituted by one or more substituents selectedindependently from R³; R¹ is a branched or unbranched C₄₋₂₄ alkyl, abranched or unbranched C₄₋₂₄ alkenyl, a branched or unbranched C₄₋₂₄oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R³; R² is a branched or unbranched C₄₋₂₄ alkyl, abranched or unbranched C₄₋₂₄ alkenyl, a branched or unbranched C₄₋₃₀oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R³; and R³ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl,C₁₋₆ heteroalkyl, C₂₋₆ alkenyl, or C₂₋₆ heteroalkenyl.

In some embodiments of the first aspect, X¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄alkenylene, each of which is optionally substituted by one or moresubstituents selected independently from R³; R¹ is a branched C₄₋₂₀alkyl, a branched C₄₋₂₀ alkenyl, a branched C₄₋₂₀ oxyalkyl, or abranched C₄₋₂₀ oxyalkenyl, each of which is optionally substituted byone or more substituents selected independently from R³; R² is abranched C₄₋₂₀ alkyl, a branched C₄₋₂₀ alkenyl, a branched C₄₋₂₀oxyalkyl, or a branched C₄₋₂₀ oxyalkenyl, each of which is optionallysubstituted by one or more substituents selected independently from R³;and R³ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, or C₂₋₆ heteroalkenyl.

In a second aspect, the disclosure provides plasticizer compositions,including a compound of formula (II):

wherein: X¹¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene, each of which isoptionally substituted by one or more substituents selectedindependently from R¹³; R¹¹ is a branched or unbranched C₄₋₂₀ alkyl, abranched or unbranched C₄₋₂₀ alkenyl, a branched or unbranched C₄₋₂₀oxyalkyl, or a branched or unbranched C₄₋₂₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R¹³; R¹² is a branched or unbranched C₄₋₂₀ alkyl, abranched or unbranched C₄₋₂₀ alkenyl, a branched or unbranched C₄₋₂₀oxyalkyl, or a branched or unbranched C₄₋₂₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R¹³; and R¹³ is a halogen atom, —OH, —NH₂, C₁₋₆alkyl, C₁₋₆ heteroalkyl, C₂₋₆ alkenyl, or C₂₋₆ heteroalkenyl.

In a third aspect, the disclosure provides polymer compositionscomprising: a polymeric resin and a plasticizer composition of thesecond aspect.

In a fourth aspect, the disclosure provides methods of increasing theplasticity of a polymeric resin, including: providing a polymeric resin;and contacting the polymeric resin with the plasticizer composition ofthe second aspect.

In a fifth aspect, the disclosure provides methods of lowering the glasstransition temperature (T_(g)) of a polymeric resin, including:providing a polymeric resin; and contacting the polymeric resin with theplasticizer composition of the second aspect.

In a sixth aspect, the disclosure provides a laminated article,comprising: a first transparent layer; and a second transparent layerdisposed on the first transparent layer, the second transparent layercomprising a polymer composition of the third aspect. In someembodiments, the first transparent layer is a glass sheet. In somefurther embodiments, the laminated article includes a third transparentlayer disposed on the second transparent layer opposite the firsttransparent layer. In some such embodiments, the third transparent layeris a glass sheet.

In a seventh aspect, the disclosure provides a laminated article,comprising: a first transparent layer having a photovoltaic cell (or aportion of a photovoltaic cell) disposed thereon; and a secondtransparent layer disposed on the first transparent layer, the secondtransparent layer comprising a polymer composition of the third aspect.In some embodiments, the first transparent layer is a glass sheet. Insome further embodiments, the laminated article includes a thirdtransparent layer disposed on the second transparent layer opposite thefirst transparent layer. In some such embodiments, the third transparentlayer is a glass sheet.

In a eighth aspect, the disclosure provides a laminated article,comprising: a first transparent layer; and a second transparent layerdisposed on the first transparent layer, the second transparent layercomprising a polymer composition of the third aspect and one or moreelectrochromic materials. In some embodiments, the first transparentlayer is a glass sheet. In some further embodiments, the laminatedarticle includes a third transparent layer disposed on the secondtransparent layer opposite the first transparent layer. In some suchembodiments, the third transparent layer is a glass sheet.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

FIG. 1 shows a non-limiting example of a compound of certain embodimentsdisclosed herein, wherein: X¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene,each of which is optionally substituted; R¹ is a branched or unbranchedC₄₋₂₄ alkyl, a branched or unbranched C₄₋₂₄ alkenyl, a branched orunbranched C₄₋₂₄ oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl,each of which is optionally substituted; R² is a branched or unbranchedC₄₋₂₄ alkyl, a branched or unbranched C₄₋₂₄ alkenyl, a branched orunbranched C₄₋₃₀ oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl,each of which is optionally substituted.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “polymer” refers to a substance having a chemicalstructure that includes the multiple repetition of constitutional unitsformed from substances of comparatively low relative molecular massrelative to the molecular mass of the polymer. The term “polymer”includes soluble and/or fusible molecules having chains of repeat units,and also includes insoluble and infusible networks. As used herein, theterm “polymer” can include oligomeric materials, which have only a few(e.g., 5-100) constitutional units

As used herein, “monomer” refers to a substance that can undergo apolymerization reaction to contribute constitutional units to thechemical structure of a polymer.

As used herein, “copolymer” refers to a polymer having constitutionalunits formed from more than one species of monomer.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “hydrocarbon” refers to an organic group composed ofcarbon and hydrogen, which can be saturated or unsaturated, and caninclude aromatic groups. The term “hydrocarbyl” refers to a monovalentor polyvalent hydrocarbon moiety.

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms; and “C_(x-y)”, which refers to a group or compoundcontaining from x to y, inclusive, carbon atoms. For example, “C₁₋₆alkyl” represents an alkyl chain having from 1 to 6 carbon atoms and,for example, includes, but is not limited to, methyl, ethyl, n-propyl,isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl,n-pentyl, neopentyl, and n-hexyl. As a further example, a “C₄₋₁₀ alkene”refers to an alkene molecule having from 4 to 10 carbon atoms, and, forexample, includes, but is not limited to, 1-butene, 2-butene, isobutene,1-pentene, 1-hexene, 3-hexene, 1-heptene, 3-heptene, 1-octene, 4-octene,1-nonene, 4-nonene, and 1-decene.

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins includealpha-olefins, wherein the unsaturated carbon-carbon bond is present atone end of the compound. Low-molecular-weight olefins may also includedienes or trienes. Low-molecular-weight olefins may also includeinternal olefins or “low-molecular-weight internal olefins.” In certainembodiments, the low-molecular-weight internal olefin is in the C₄₋₁₄range. Examples of low-molecular-weight olefins in the C₂₋₆ rangeinclude, but are not limited to: ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1,4-pentadiene,1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, andcyclohexene. Non-limiting examples of low-molecular-weight olefins inthe C₇₋₉ range include 1,4-heptadiene, 1-heptene, 3,6-nonadiene,3-nonene, 1,4,7-octatriene. Other possible low-molecular-weight olefinsinclude styrene and vinyl cyclohexane. In certain embodiments, it ispreferable to use a mixture of olefins, the mixture comprising linearand branched low-molecular-weight olefins in the C₄₋₁₀ range. Olefins inthe C₄₋₁₀ range can also be referred to as “short-chain olefins,” whichcan be either branched or unbranched. In one embodiments, it may bepreferable to use a mixture of linear and branched C₄ olefins (i.e.,combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C₁₁₋₁₄ may be used.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin ester”or “olefinic ester compounds.” Further, a “terminal olefinic estercompound” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, “acid,” “acids,” “carboxylic acid,” or “carboxylicacids” refer to compounds having the general formula: R—COOH, wherein Rdenotes any organic moiety (such as alkyl, aryl, or silyl groups),including those bearing heteroatom-containing substituent groups. Incertain embodiments, R denotes alkyl, alkenyl, aryl, or alcohol groups.In certain embodiments, the term “acids” or “carboxylic acids” may referto a group of compounds with the general formula described above,wherein the compounds have different carbon lengths.

As used herein, “alcohol” or “alcohols” refer to compounds having thegeneral formula: R—OH, wherein R denotes any organic moiety (such asalkyl, aryl, or silyl groups), including those bearingheteroatom-containing substituent groups. In certain embodiments, Rdenotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments,the term “alcohol” or “alcohols” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. As used herein, the term “alkanol” refers toalcohols where R is an alkyl group.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y) alkyl,” which refersto an alkyl group, as herein defined, containing from x to y, inclusive,carbon atoms. Thus, “C₁₋₆ alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group. Also, in someinstances, one or more of the carbon atoms in the alkyl or alkylenegroup can be replaced by a heteroatom (e.g., selected from nitrogen,oxygen, or sulfur, including N-oxides, sulfur oxides, and sulfurdioxides, where feasible), and is referred to as a “heteroalkyl” or“heteroalkylene” group, respectively. Non-limiting examples include“oxyalkyl” or “oxyalkylene” groups, which are groups of the followingformulas: -[-(alkylene)-O-]_(x)-alkyl, or-[-(alkylene)-O-]_(x)-alkylene-, respectively, where x is 1 or more,such as 1, 2, 3, 4, 5, 6, 7, or 8.

As used herein, “alkenyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number ofcarbon atoms in an alkenyl group is represented by the phrase “C_(x-y)alkenyl,” which refers to an alkenyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₂₋₆ alkenyl”represents an alkenyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethenyl, 2-propenyl,2-butenyl, and 3-butenyl. In some instances, the “alkenyl” group can bedivalent, in which case the group can alternatively be referred to as an“alkenylene” group. Also, in some instances, one or more of thesaturated carbon atoms in the alkenyl or alkenylene group can bereplaced by a heteroatom (e.g., selected from nitrogen, oxygen, orsulfur, including N-oxides, sulfur oxides, and sulfur dioxides, wherefeasible), and is referred to as a “heteroalkenyl” or “heteroalkenylene”group, respectively. Non-limiting examples include “oxyalkenyl” or“oxyalkenylene” groups, which are groups of the following formulas:—[—(R^(f))—O—]_(x)—R^(g), or —[—(R^(f))—O—]_(x)—R^(h)—, respectively,where x is 1 or more, such as 1, 2, 3, 4, 5, 6, 7, or 8, and R^(f),R^(g), and R^(h) are independently alkyl/alkylene or alkenyl/alkenylenegroups, provided that each such “oxyalkenyl” or “oxyalkenylene” groupcontains at least one carbon-carbon double bond.

As used herein, the term “branched,” for example, in reference to analkyl or alkenyl group, refers to the presence of one or more carbonatoms having three or four connections to other carbon atoms. Bycontrast, the term “unbranched” refers to groups not having any carbonatoms with three or four connections to other carbon atoms. For example,groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl arebranched, and groups such as n-propyl and n-butyl are unbranched. Insome instances, it may be desirable to refer to a position for thebranching, such as in the alcoholic portion of an ester. In suchinstances, the carbon atom immediately adjacent to the oxygen atom onthe alcoholic side of the ester is the 1-position, the next in the2-position, and so on. Thus, the alkyl group of sec-butyl alcohol orisopropyl alcohol is said to be branched at the 1-position, and thealkyl group of isobutyl alcohol is said to be branched at the 2-positionand not branched at the 1-position, and so forth. The same principlesapply to alkenyl groups, as the double bond does not count as 2connections. Thus, groups like 9-octedenenyl are said to be unbranched,while a group like 1-methyl-9-octadenenyl is said to be branched, i.e.,at the 1-position.

As used herein, “halogen” or “halo” refers to a fluorine, chlorine,bromine, and/or iodine atom. In some embodiments, the terms refer tofluorine and/or chlorine.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week. As used herein, the phrases “substituted with one ormore . . . ” or “substituted one or more times . . . ” refer to a numberof substituents that equals from one to the maximum number ofsubstituents possible based on the number of available bonding sites,provided that the above conditions of stability and chemical feasibilityare met.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Branched-Chain Diesters of Alkanedioic Acids and Alkenedioic Acids

In certain aspects, the disclosure provides compounds that arebranched-chain diesters (i.e., formed from branched-chain alcohols) ofalkanedioic acids and/or alkenedioic acids, wherein the alkanedioicacids and/or alkenedioic acids have at least 13 carbon atoms, or atleast 14 carbon atoms, or at least 16 carbon atoms, up to 24 carbonatoms. In some embodiments the alkanedioic acids and/or alkenedioicacids have 18 carbon atoms, such as octadecanedioic acid,9-octadecenedioic acid, and the like.

In some embodiments, the branched-chain diesters are compounds offormula (I):

wherein: X¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene, each of which isoptionally substituted by one or more substituents selectedindependently from R³; R¹ is a branched or unbranched C₄₋₂₄ alkyl, abranched or unbranched C₄₋₂₄ alkenyl, a branched or unbranched C₄₋₃₀oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R³; R² is a branched or unbranched C₄₋₂₄ alkyl, abranched or unbranched C₄₋₂₄ alkenyl, a branched or unbranched C₄₋₃₀oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R³; and R³ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl,C₁₋₆ heteroalkyl, C₂₋₆ alkenyl, or C₂₋₆ heteroalkenyl.

In some embodiments, X¹ is C₁₁₋₂₄ alkylene, optionally substituted oneor more times with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹ is C₁₂₋₂₄ alkylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹ is C₁₂₋₂₀ alkylene,optionally substituted one or more times with substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, X¹ isC₁₄₋₂₀ alkylene, optionally substituted one or more times withsubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, X¹ is C₁₄₋₁₈ alkylene, optionally substituted one or moretimes with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹ is C₁₆ alkylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹ is —(CH₂)₁₂—,—(CH₂)₁₄—, —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₂₀—, or —(CH₂)₂₂—. In some suchembodiments, X¹ is —(CH₂)₁₄—, —(CH₂)₁₆—, or —(CH₂)₂₀—. In someembodiments, X¹ is —(CH₂)₁₆—.

In some embodiments, X¹ is C₁₁₋₂₄ alkenylene, optionally substituted oneor more times with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹ is C₁₂₋₂₄ alkenylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹ is

C₁₂₋₂₀ alkenylene, optionally substituted one or more times withsubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, X¹ is C₁₄₋₂₀ alkenylene, optionally substituted one or moretimes with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹ is C₁₄₋₁₈ alkenylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹ is C₁₆ alkenylene,optionally substituted one or more times with substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, X¹ is—(CH₂)₇—CH═CH═(CH₂)₇—. In some other embodiments, X¹ is—(CH₂)₅—CH═CH═(CH₂)₅—. In some other embodiments, X¹ is—(CH₂)₉—CH═CH═(CH₂)₉—.

In certain further embodiments of any of the above embodiments, R¹ is anunbranched C₄₋₂₄, which is optionally substituted by one or moresubstituents selected independently from R³. In some furtherembodiments, R¹ is an unbranched C₄₋₂₀ alkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R¹ is butyl, pentyl, hexyl,heptyl, or octyl.

In some embodiments, R¹ is a branched C₄₋₂₄ alkyl, which is optionallysubstituted by one or more substituents selected independently from R³.In some further embodiments, R¹ is a branched C₄₋₂₀ alkyl, whichcomprises branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹ is abranched C₄₋₂₀ alkyl, which comprises branching at the 2-position of thealkyl moiety, and which is optionally substituted by one or moresubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, R¹ is a branched C₄₋₂₀ alkyl, which comprises branching atthe 3-position of the alkyl moiety, and which is optionally substitutedby one or more substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, R¹ is a branched C₄₋₂₀ alkyl, which hasno branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹ is2-methylpentyl, 2-ethylhexyl, 2-butyloctyl, and 3-methylbutyl.

In some embodiments, R¹ is C₄₋₃₀ oxyalkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R¹ is C₄₋₂₄ oxyalkyl, which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹ is—(CH₂—CH₂—O)₁₋₁₄—R^(x), or —(CH₂—CH₂—O)₁₋₁₂—R^(x), where R^(x) is C₁₋₆unbranched alkyl. In some embodiments, R^(x) is methyl. In some otherembodiments, R^(x) is ethyl. In some embodiments, R¹ is —CH₂—CH₂—O—CH₃.In some embodiments, R¹ is —(CH₂—CH₂—O)₂—CH₃. In some embodiments, R¹ is—(CH₂—CH₂—O)₃—CH₃. In some embodiments, R¹ is —(CH₂—CH₂—O)₄—CH₃. In someembodiments, R¹ is —(CH₂—CH₂—O)₅—CH₃. In some embodiments, R¹ is—(CH₂—CH₂—O)₆—CH₃. In some embodiments, R¹ is —(CH₂—CH₂—O)₇—CH₃. In someembodiments, R¹ is —(CH₂—CH₂—O)₈—CH₃. In some embodiments, R¹ is—(CH₂—CH₂—O)₉—CH₃. In some embodiments, R¹ is —(CH₂—CH₂—O)₁₀—CH₃. Insome embodiments, R¹ is —(CH₂—CH₂—O)₁₁—CH₃. In some embodiments, R¹ is—(CH₂—CH₂—O)₁₂—CH₃.

In certain further embodiments of any of the above embodiments, R² is anunbranched C₄₋₂₄, which is optionally substituted by one or moresubstituents selected independently from R³. In some furtherembodiments, R² is an unbranched C₄₋₂₀ alkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R² is butyl, pentyl, hexyl,heptyl, or octyl.

In some embodiments, R² is a branched C₄₋₂₄ alkyl, which is optionallysubstituted by one or more substituents selected independently from R³.In some further embodiments, R² is a branched C₄₋₂₀ alkyl, whichcomprises branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R² is abranched C₄₋₂₀ alkyl, which comprises branching at the 2-position of thealkyl moiety, and which is optionally substituted by one or moresubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, R² is a branched C₄₋₂₀ alkyl, which comprises branching atthe 3-position of the alkyl moiety, and which is optionally substitutedby one or more substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, R² is a branched C₄₋₂₀ alkyl, which hasno branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R² is2-methylpentyl, 2-ethylhexyl, 2-butyloctyl, and 3-methylbutyl.

In some embodiments, R² is C₄₋₃₀ oxyalkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R² is C₄₋₂₄ oxyalkyl, which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R² is—(CH₂—CH₂—O)₁₋₁₄—R^(x′) or —(CH₂—CH₂—O)₁₋₁₂—R^(x′), where R^(x′) is C₁₋₆unbranched alkyl. In some embodiments, R^(x′) is methyl. In some otherembodiments, R^(x′) is ethyl. In some embodiments, R² is —CH₂—CH₂—O—CH₃.In some embodiments, R² is —(CH₂—CH₂—O)₂—CH₃. In some embodiments, R² is—(CH₂—CH₂—O)₃—CH₃. In some embodiments, R² is —(CH₂—CH₂—O)₄—CH₃. In someembodiments, R² is —(CH₂—CH₂—O)₅—CH₃. In some embodiments, R² is—(CH₂—CH₂—O)₆—CH₃. In some embodiments, R² is —(CH₂—CH₂—O)₇—CH₃. In someembodiments, R² is —(CH₂—CH₂—O)₈—CH₃. In some embodiments, R² is—(CH₂—CH₂—O)₉—CH₃. In some embodiments, R² is —(CH₂—CH₂—O)₁₀—CH₃. Insome embodiments, R² is —(CH₂—CH₂—O)₁₁—CH₃. In some embodiments, R² is—(CH₂—CH₂—O)₁₂—CH₃.

In some embodiments of any of the above embodiments, R¹ and R² are thesame. In some other embodiments, R¹ and R² are not the same.

The compounds disclosed above are not limited to any particular use orapplication. In some embodiments, they can be suitable for use asplasticizers, e.g., for polymer resins. They can be suitable for otheruses as well.

Plasticizer Compositions

In certain aspects, the disclosure provides plasticizer compositionsthat include diester compounds. In some embodiments, at least oneportion (e.g., the acid portion, one or both alcohol portions, or boththe acid portion and one or both alcohol portions) is branched. In someembodiments, the diester compounds are branched-chain diesters (i.e.,formed from branched-chain alcohols) of alkanedioic acids and/oralkenedioic acids, wherein the alkanedioic acids and/or alkenedioicacids have at least 13 carbon atoms, or at least 14 carbon atoms, or atleast 16 carbon atoms, up to 24 carbon atoms. In some embodiments thealkanedioic acids and/or alkenedioic acids have 18 carbon atoms, such asoctadecanedioic acid, 9-octadecenedioic acid, and the like.

In some embodiments, the plasticizer compositions, include a compound offormula (II):

wherein: X¹¹ is C₁₁₋₂₄ alkylene or C₁₁₋₂₄ alkenylene, each of which isoptionally substituted by one or more substituents selectedindependently from R¹³; R¹¹ is a branched or unbranched C₄₋₂₄ alkyl, abranched or unbranched C₄₋₂₄ alkenyl, a branched or unbranched C₄₋₃₀oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R¹³; R¹² is a branched or unbranched C₄₋₂₄ alkyl, abranched or unbranched C₄₋₂₄ alkenyl, a branched or unbranched C₄₋₃₀oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each of which isoptionally substituted by one or more substituents selectedindependently from R¹³; and R¹³ is a halogen atom, —OH, —NH₂, C₁₋₆alkyl, C₁₋₆ heteroalkyl, C₂₋₆ alkenyl, or C₂₋₆ heteroalkenyl.

In some embodiments, X¹¹ is C₁₁₋₂₄ alkylene, optionally substituted oneor more times with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹¹ is C₁₂₋₂₄ alkylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹¹ is C₁₂₋₂₀ alkylene,optionally substituted one or more times with substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, X¹¹ isC₁₄₋₂₀ alkylene, optionally substituted one or more times withsubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, X¹¹ is C₁₄₋₁₈ alkylene, optionally substituted one or moretimes with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹¹ is C₁₆ alkylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹¹ is —(CH₂)₁₂—,—(CH₂)₁₄—, —(CH₂)₁₆—, —(CH₂)₁₈—, —(CH₂)₂₀—, or —(CH₂)₂₂—. In some suchembodiments, X¹¹ is —(CH₂)₁₄—, —(CH₂)₁₆—, or —(CH₂)₂₀—. In someembodiments, X¹¹ is —(CH₂)₁₆—.

In some embodiments, X¹¹ is C₁₁₋₂₄ alkenylene, optionally substitutedone or more times with substituents selected independently from —OH andC₁₋₆ alkyloxy. In some embodiments, X¹¹ is C₁₂₋₂₄ alkenylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹¹ is C₁₂₋₂₀alkenylene, optionally substituted one or more times with substituentsselected independently from —OH and C₁₋₆ alkyloxy. In some embodiments,X¹¹ is C₁₄₋₂₀ alkenylene, optionally substituted one or more times withsubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, X¹¹ is C₁₄₋₁₈ alkenylene, optionally substituted one ormore times with substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, X¹¹ is C₁₆ alkenylene, optionallysubstituted one or more times with substituents selected independentlyfrom —OH and C₁₋₆ alkyloxy. In some embodiments, X¹¹ is—(CH₂)₇—CH═CH═(CH₂)₇—. In some other embodiments, X¹¹ is—(CH₂)₅—CH═CH═(CH₂)₅—. In some other embodiments, X¹¹ is—(CH₂)₉—CH═CH═(CH₂)₉—.

In certain further embodiments of any of the above embodiments, R¹¹ isan unbranched C₄₋₂₄, which is optionally substituted by one or moresubstituents selected independently from R¹³. In some furtherembodiments, R¹¹ is an unbranched C₄₋₂₀ alkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R¹¹ is butyl, pentyl, hexyl,heptyl, or octyl.

In some embodiments, R¹¹ is a branched C₄₋₂₄ alkyl, which is optionallysubstituted by one or more substituents selected independently from R¹³.In some further embodiments, R¹¹ is a branched C₄₋₂₀ alkyl, whichcomprises branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹¹ is abranched C₄₋₂₀ alkyl, which comprises branching at the 2-position of thealkyl moiety, and which is optionally substituted by one or moresubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, R¹¹ is a branched C₄₋₂₀ alkyl, which comprises branching atthe 3-position of the alkyl moiety, and which is optionally substitutedby one or more substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, R¹¹ is a branched C₄₋₂₀ alkyl, which hasno branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹¹ is2-methylpentyl, 2-ethylhexyl, 2-butyloctyl, and 3-methylbutyl.

In some embodiments, R¹¹ is C₄₋₃₀ oxyalkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R¹¹ is C₄₋₂₄ oxyalkyl, which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹¹ is—(CH₂—CH₂—O)₁₋₁₄—R^(y) or —(CH₂—CH₂—O)₁₋₁₂—R^(y), where R^(y) is C₁₋₆unbranched alkyl. In some embodiments, R^(y) is methyl. In some otherembodiments, R^(y) is ethyl. In some embodiments, R¹¹ is —CH₂—CH₂—O—CH₃.In some embodiments, R¹¹ is —(CH₂—CH₂—O)₂—CH₃. In some embodiments, R¹¹is —(CH₂—CH₂—O)₃—CH₃. In some embodiments, R¹¹ is —(CH₂—CH₂—O)₄—CH₃. Insome embodiments, R¹¹ is —(CH₂—CH₂—O)₅—CH₃. In some embodiments, R¹¹ is—(CH₂—CH₂—O)₆—CH₃. In some embodiments, R¹¹ is —(CH₂—CH₂—O)₇—CH₃. Insome embodiments, R¹¹ is —(CH₂—CH₂—O)₈—CH₃. In some embodiments, R¹¹ is—(CH₂—CH₂—O)₉—CH₃. In some embodiments, R¹¹ is —(CH₂—CH₂—O)₁₀—CH₃. Insome embodiments, R¹¹ is —(CH₂—CH₂—O)₁₁—CH₃. In some embodiments, R¹¹ is—(CH₂—CH₂—O)₁₂—CH₃.

In certain further embodiments of any of the above embodiments, R¹² isan unbranched C₄₋₂₄, which is optionally substituted by one or moresubstituents selected independently from R¹³. In some furtherembodiments, R¹² is an unbranched C₄₋₂₀ alkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R¹² is butyl, pentyl, hexyl,heptyl, or octyl.

In some embodiments, R¹² is a branched C₄₋₂₄ alkyl, which is optionallysubstituted by one or more substituents selected independently from R¹³.In some further embodiments, R¹² is a branched C₄₋₂₀ alkyl, whichcomprises branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹² is abranched C₄₋₂₀ alkyl, which comprises branching at the 2-position of thealkyl moiety, and which is optionally substituted by one or moresubstituents selected independently from —OH and C₁₋₆ alkyloxy. In someembodiments, R¹² is a branched C₄₋₂₀ alkyl, which comprises branching atthe 3-position of the alkyl moiety, and which is optionally substitutedby one or more substituents selected independently from —OH and C₁₋₆alkyloxy. In some embodiments, R¹² is a branched C₄₋₂₀ alkyl, which hasno branching at the 1-position of the alkyl moiety, and which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹² is2-methylpentyl, 2-ethylhexyl, 2-butyloctyl, and 3-methylbutyl.

In some embodiments, R¹² is C₄₋₃₀ oxyalkyl, which is optionallysubstituted by one or more substituents selected independently from —OHand C₁₋₆ alkyloxy. In some embodiments, R¹² is C₄₋₂₄ oxyalkyl, which isoptionally substituted by one or more substituents selectedindependently from —OH and C₁₋₆ alkyloxy. In some embodiments, R¹² is—(CH₂—CH₂—O)₁₋₁₄—R^(y′) or —(CH₂—CH₂—O)₁₋₁₂—R^(y), where R^(y) is C₁₋₆unbranched alkyl. In some embodiments, R^(y′) is methyl. In someembodiments, R^(y) is ethyl. In some embodiments, R¹² is —CH₂—CH₂—O—CH₃.In some embodiments, R¹² is —(CH₂—CH₂—O)₂—CH₃. In some embodiments, R¹²is —(CH₂—CH₂—O)₃—CH₃. In some embodiments, R¹² is —(CH₂—CH₂—O)₄—CH₃. Insome embodiments, R¹² is —(CH₂—CH₂—O)₅—CH₃. In some embodiments, R¹² is—(CH₂—CH₂—O)₆—CH₃. In some embodiments, R¹² is —(CH₂—CH₂—O)₇—CH₃. Insome embodiments, R¹² is —(CH₂—CH₂—O)₈—CH₃. In some embodiments, R¹² is—(CH₂—CH₂—O)₉—CH₃. In some embodiments, R¹² is —(CH₂—CH₂—O)₁₀—CH₃. Insome embodiments, R¹² is —(CH₂—CH₂—O)₁₁—CH₃. In some embodiments, R¹² is—(CH₂—CH₂—O)₁₂—CH₃.

In some embodiments of any of the above embodiments, R¹¹ and R¹² are thesame. In some other embodiments, R¹¹ and R¹² are not the same.

In some embodiments, the plasticizer composition consists of one ordiesters according to any of the above embodiments. In some embodiments,the plasticizer composition consists essentially of one or diestersaccording to any of the above embodiments.

In some embodiments, the plasticizer composition includes one or moreadditional components, i.e., in addition to one of more of the diestersof any of the preceding embodiments. For example, in some embodiments,the plasticizer composition includes one or more additionalplasticizers. Any suitable plasticizers can be used. For example, insome embodiments, the one or more additional plasticizers areplasticizers that are compatible for use with polymeric resins,including, but not limited to, phthalates, adipates, trimellitic esters,phosphate esters, sebacates, azelates, sulphonates, epoxidized fattyacid esters, or any combination thereof. Such compounds include, but arenot limited to, benzenedicarboxylic esters, citraconic esters,2-hydroxy-1,2,3-propanetricarboxylic esters, malonic esters, succinates,vegetable and animal oils, benzoic esters, triethylene glycoldihexanoate, tetraethylene glycol diheptanoate, linear alkylbenzenes(LABs), branched alkylbenzenes (BABs), polyethylene glycols,polyethylene glycol ethers, polypropylene glycols, polypropylene glycolethers, or any combinations thereof.

In some embodiments, the plasticizer can include one or more additionaladditives. Any suitable additives can be used, so long as they aregenerally compatible with the plasticizing components of thecomposition. In some embodiments, the plasticizer composition includesmetal oxides, such as silica, alumina, titania, and the like;antioxidants; colorants; color modifiers; diluents; or any combinationsthereof.

Polymer Compositions

In certain aspects, the disclosure provides polymer compositions thatinclude a polymeric resin and a plasticizer composition of any of theembodiments disclosed above. Any suitable polymeric resin can be used.For example, in some embodiments, the polymeric resin is: a vinylchloride resin, such as polyvinyl chloride (PVC); polyvinyl butyral(PVB); a polysulfide; a polyurethane; an acrylic resin; anepichlorohydrins; nitrile rubber; chloro sulfonated polyethylene;chlorinated polyethylene; polychloroprene; styrene butadiene rubber;natural rubber; synthetic rubber; EPDM rubber; propylene-based polymers,such as polypropylene; ethylene-based polymers, such as polyethylene; orany combinations, blends, or copolymers thereof. In some embodiments,the polymeric resin is polyvinyl chloride (PVC) or any blends orcopolymers thereof. In some other embodiments, the polymeric resin ispolyvinyl butyral (PVB) or any blends of copolymers thereof.

In some embodiments, the polymer composition can include one or moreadditives in addition to the polymeric resin and the plasticizercomposition. Any suitable additives can be used. For example, in someembodiments, the polymer composition can include a filler (e.g., calciumcarbonate, clays, and metal oxides, such as silica, alumina, ortitania), a flame retardant, a heat stabilizer, an anti-drip agent, acolorant, a lubricant, a low molecular weight polyethylene, a hinderedamine light stabilizer, a UV light absorber, a curing agent, a booster,a retardant, a processing aid, a coupling agent, an antistatic agent, anucleating agent, a slip agent, a viscosity control agent, a tackifier,an anti-blocking agent, a surfactant, an extender oil, an acidscavenger, a metal deactivator, metal soap stabilizers (e.g., zincstearate or mixed metal stabilizers containing Ca, Zn, Mg, Sn, and anycombination thereof), an antioxidant (e.g., a phenolic antioxidant), aprocessing aid, or any combinations thereof.

Methods of Making Diesters

The diesters disclosed above can be made by conventional means. Forexample, in some embodiments, the diesters are made by reacting adibasic acid with an alcohol or a mixture of alcohols to provide thedibasic ester by condensation. In some instances, diesters can also bemade by transesterification, where a dibasic ester, such as a dimethyldibasic ester is reacted with a longer-chain alcohol or mixture oflonger-chain alcohols to provide the dibasic ester.

Derivation from Renewable Sources

The compounds employed in any of the aspects or embodiments disclosedherein can, in certain embodiments, be derived from renewable sources,such as from various natural oils or their derivatives. Any suitablemethods can be used to make these compounds from such renewable sources.Suitable methods include, but are not limited to, fermentation,conversion by bioorganisms, and conversion by metathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275595, and 2014/0275681, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin (or short-chainolefin) is in the C₂₋₆ range. As a non-limiting example, in oneembodiment, the low-molecular-weight olefin may comprise at least oneof: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. In someembodiments, the short-chain olefin is 1-butene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, the unsaturatedesters may be derived from a natural oil feedstock, in addition to othervaluable compositions. Moreover, in some embodiments, a number ofvaluable compositions can be targeted through the self-metathesisreaction of a natural oil feedstock, or the cross-metathesis reaction ofthe natural oil feedstock with a low-molecular-weight olefin ormid-weight olefin, in the presence of a metathesis catalyst. Suchvaluable compositions can include fuel compositions, detergents,surfactants, and other specialty chemicals. Additionally,transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, multiple metathesis reactions can also beemployed. In some embodiments, the multiple metathesis reactions occursequentially in the same reactor. For example, a glyceride containinglinoleic acid can be metathesized with a terminal lower alkene (e.g.,ethylene, propylene, 1-butene, and the like) to form 1,4-decadiene,which can be metathesized a second time with a terminal lower alkene toform 1,4-pentadiene. In other embodiments, however, the multiplemetathesis reactions are not sequential, such that at least one otherstep (e.g., transesterification, hydrogenation, etc.) can be performedbetween the first metathesis step and the following metathesis step.These multiple metathesis procedures can be used to obtain products thatmay not be readily obtainable from a single metathesis reaction usingavailable starting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

For example, multiple metathesis can be employed to make the dibasicacid compounds used to make the diesters disclosed herein. In someembodiments, alkyl (e.g., methyl) esters of 9-decenoic acid,9-undecenoic acid, 9-dodecenoic acid, or any combination thereof, can bereacted in a self-metathesis reaction or a cross-metathesis to generatevarious unsaturated dibasic alkyl esters, such as dimethyl9-octadecendioate. Such compounds can then be converted to dibasic acidsby hydrolysis or via saponification followed by acidification. If asaturated dibasic acid is desired, the compound can be hydrogenated,either before conversion to the acid or after. Dibasic acids of otherchain lengths can be made by analogous means.

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described below with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, terminal olefinsand internal olefins may be derived from a natural oil feedstock, inaddition to other valuable compositions. Moreover, in some embodiments,a number of valuable compositions can be targeted through theself-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, the methods disclosed herein can employmultiple metathesis reactions. In some embodiments, the multiplemetathesis reactions occur sequentially in the same reactor. Forexample, a glyceride containing linoleic acid can be metathesized with aterminal lower alkene (e.g., ethylene, propylene, 1-butene, and thelike) to form 1,4-decadiene, which can be metathesized a second timewith a terminal lower alkene to form 1,4-pentadiene. In otherembodiments, however, the multiple metathesis reactions are notsequential, such that at least one other step (e.g.,transesterification, hydrogenation, etc.) can be performed between thefirst metathesis step and the following metathesis step. These multiplemetathesis procedures can be used to obtain products that may not bereadily obtainable from a single metathesis reaction using availablestarting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The rector design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

The metathesis reaction can be run under any desired pressure. In someinstances, it may be desirable to maintain a total pressure that is highenough to keep the cross-metathesis reagent in solution. Therefore, asthe molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa),or greater than 1 atm (100 kPa). In some embodiments, the reactionpressure is no more than about 70 atm (7000 kPa), or no more than about30 atm (3000 kPa). In some embodiments, the pressure for the metathesisreaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

Methods of Increasing the Plasticity of a Resin

In certain aspects, the disclosure provides methods of increasing theplasticity of a polymeric resin, comprising: providing a polymericresin; and contacting the polymeric resin with the plasticizercomposition of any one of the above embodiments.

In some embodiments, the contacting of the polymeric resin with theplasticizer composition comprises contacting the polymeric resin with aplasticizing effective amount of the plasticizer composition. Aplasticizing effective amount will vary depending on a number offactors, including, but not limited to, the chemical structure of theresin, the desired amount of plasticity, the chemical makeup of theplasticizing composition, and the like.

Any suitable resin can be plasticized. In some embodiments, thepolymeric resin is: a vinyl chloride resin, such as polyvinyl chloride(PVC); polyvinyl butyral (PVB); a polysulfide; a polyurethane; anacrylic resin; an epichlorohydrins; nitrile rubber; chloro sulfonatedpolyethylene; chlorinated polyethylene; polychloroprene; styrenebutadiene rubber; natural rubber; synthetic rubber; EPDM rubber;propylene-based polymers, such as polypropylene; ethylene-basedpolymers, such as polyethylene; or any combinations, blends, orcopolymers thereof. In some embodiments, the polymeric resin ispolyvinyl chloride (PVC). In some embodiments, the polymeric resin ispolyvinyl butyral (PVB).

Methods of Lowering the Glass Transition Temperature of a Resin

In certain aspects, the disclosure provides methods of lowering theglass transition temperature (T_(g)) of a polymeric resin, comprising:providing a polymeric resin; and contacting the polymeric resin with theplasticizer composition of any one of the above embodiments.

Any suitable amount of the plasticizer composition can be used. Theamount will vary depending on a number of factors, including, but notlimited to, the chemical structure of the resin, the desired degree oflowering, the chemical makeup of the plasticizing composition, and thelike.

Any suitable resin can be subjected to such treatment. In someembodiments, the polymeric resin is: a vinyl chloride resin, such aspolyvinyl chloride (PVC); polyvinyl butyral (PVB); a polysulfide; apolyurethane; an acrylic resin; an epichlorohydrins; nitrile rubber;chloro sulfonated polyethylene; chlorinated polyethylene;polychloroprene; styrene butadiene rubber; natural rubber; syntheticrubber; EPDM rubber; propylene-based polymers, such as polypropylene;ethylene-based polymers, such as polyethylene; or any combinations,blends, or copolymers thereof. In some embodiments, the polymeric resinis polyvinyl chloride (PVC). In some embodiments, the polymeric resin ispolyvinyl butyral (PVB).

Laminated Articles

In a certain aspects and embodiments, the disclosure provides alaminated article, comprising: a first transparent layer; and a secondtransparent layer disposed on the first transparent layer, the secondtransparent layer comprising a polymer composition.

Any suitable transparent material can be used as the first transparentlayer. Examples include, but are not limited to, polycarbonate andvarious kinds of glass. In some embodiments, the first transparent layeris a glass sheet.

The polymer composition can include any of suitable polymer composition.Suitable polymer compositions include those disclosed above, such asthose described above that include a polymer and one or more compoundsof formula (II). In some embodiments, the second transparent layer isdisposed directly on the first transparent layer, such that there is nointervening layer. In some other embodiments, however, there can be oneor more intervening layers that separate the first transparent layerfrom the second transparent layer, such that the second transparentlayer is indirectly disposed on the first transparent layer.

In some further embodiments, the laminated article includes a thirdtransparent layer disposed on the second transparent layer opposite thefirst transparent layer. Any suitable transparent material can be usedas the third transparent layer. Examples include, but are not limitedto, polycarbonate and various kinds of glass. In some embodiments, thethird transparent layer is a glass sheet. Further, in some embodiments,the third transparent layer is disposed directly on the secondtransparent layer, such that there is no intervening layer. In someother embodiments, however, there can be one or more intervening layersthat separate the third transparent layer from the second transparentlayer, such that the second transparent layer is indirectly disposed onthe third transparent layer.

Photovoltaic Articles

In a certain aspects and embodiments, the disclosure provides alaminated article, comprising: a first transparent layer having aphotovoltaic cell (or a portion of a photovoltaic cell) disposedthereon; and a second transparent layer disposed on the firsttransparent layer, the second transparent layer comprising a polymercomposition.

Any suitable transparent material can be used as the first transparentlayer. Examples include, but are not limited to, polycarbonate andvarious kinds of glass. In some embodiments, the first transparent layeris a glass sheet.

The polymer composition can include any of suitable polymer composition.Suitable polymer compositions include those disclosed above, such asthose described above that include a polymer and one or more compoundsof formula (II). In some embodiments, the second transparent layer isdisposed directly on the first transparent layer, such that there is nointervening layer. In some other embodiments, however, there can be oneor more intervening layers that separate the first transparent layerfrom the second transparent layer, such that the second transparentlayer is indirectly disposed on the first transparent layer.

The photovoltaic cell can be any suitable photovoltaic cell, such asthose commonly known in the art. In some embodiments, the photovoltaiccell is made of a transparent material. Suitable examples of suchtransparent materials include, but are not limited to, transparentconductive polymers, indium tin oxide (ITO), and the like.

In some further embodiments, the laminated article includes a thirdtransparent layer disposed on the second transparent layer opposite thefirst transparent layer. Any suitable transparent material can be usedas the third transparent layer. Examples include, but are not limitedto, polycarbonate and various kinds of glass. In some embodiments, thethird transparent layer is a glass sheet. Further, in some embodiments,the third transparent layer is disposed directly on the secondtransparent layer, such that there is no intervening layer. In someother embodiments, however, there can be one or more intervening layersthat separate the third transparent layer from the second transparentlayer, such that the second transparent layer is indirectly disposed onthe third transparent layer.

Electrochromic Articles

In a eighth aspect, the disclosure provides a laminated article,comprising: a first transparent layer; and a second transparent layerdisposed on the first transparent layer, the second transparent layercomprising a polymer composition of the third aspect and one or moreelectrochromic materials.

Any suitable transparent material can be used as the first transparentlayer. Examples include, but are not limited to, polycarbonate andvarious kinds of glass. In some embodiments, the first transparent layeris a glass sheet.

The polymer composition can include any of suitable polymer composition.Suitable polymer compositions include those disclosed above, such asthose described above that include a polymer and one or more compoundsof formula (II). In some embodiments, the second transparent layer isdisposed directly on the first transparent layer, such that there is nointervening layer. In some other embodiments, however, there can be oneor more intervening layers that separate the first transparent layerfrom the second transparent layer, such that the second transparentlayer is indirectly disposed on the first transparent layer.

The electrochromic material can be any suitable electrochromic material,such as those commonly known in the art. In some embodiments, theelectrochromic material is made of a transparent material.

In some further embodiments, the laminated article includes a thirdtransparent layer disposed on the second transparent layer opposite thefirst transparent layer. Any suitable transparent material can be usedas the third transparent layer. Examples include, but are not limitedto, polycarbonate and various kinds of glass. In some embodiments, thethird transparent layer is a glass sheet. Further, in some embodiments,the third transparent layer is disposed directly on the secondtransparent layer, such that there is no intervening layer. In someother embodiments, however, there can be one or more intervening layersthat separate the third transparent layer from the second transparentlayer, such that the second transparent layer is indirectly disposed onthe third transparent layer.

EXAMPLES Example 1 Bis(2-buytloctyl) Octadecanedioate

Octadecanedioic acid (ODDA, 5.00 g) was added to a 100-mL three-neckedround-bottom flask. A Dean-Stark condenser was attached, followed by theaddition of toluene to the ODDA and to the trap. 2-Butyloctyl alcohol(11 mL) was added to the ODDA mixture. The flask was immediately purgedwith nitrogen gas and p-toluenesulfonic acid (0.17 g) was added. Thereaction mixture was heated to 115° C. and the reaction proceeded for 5hours. Heat was then removed and the reaction mixture was allowed tocool to 60° C., at which point aqueous NaHCO₃ (saturated) was added toachieve a neutral pH. After vigorous stirring, the organic layer wasseparated and dried over Na₂SO₄. The dried product was then subjected toa vacuum treatment to remove any residual solvent. A yellow oil wasobtained. Analysis by ¹H NMR provided the following chemical shifts:(400 MHz, CDCl₃) δ 0.85-1.10 (m, 88H), 1.20-1.38 (m, 346H), 1.40-1.50(m, 10H), 1.55 (s, 12H), 1.65 (t, 33H), 2.30 (t, 20H), 3.97 (d, 21H).Analysis by ¹³C NMR provided the following chemical shifts: (400 MHz,CDCl₃) δ C, 174.169; CH, 67.037; CH₂, 22.672, 23.003, 25.093, 26.685,28.931, 29.205, 29.326, 29.518, 29.646, 29.682, 29.702, 30.972, 31.297,31.834, 34.500, 37.286; CH₃, 14.067, 14.115.

Polyvinyl butyral (PVB) films were prepared using varying amounts ofbis(2-buytloctyl) octadecanedioate ranging from none to 40 percent byweight of the plasticizer, relative to the total weight of the polymercomposition. Table 1 shows the glass transition temperature (T_(g)) forfilms of varying amount of plasticizer incorporation.

TABLE 1 Plasticizer Loading (wt %) T_(g) (° C.) 0 76.5 10 64.5 20 63.030 57.5 40 56.0

Example 2 Bis(2-methylpentyl) Octadecanedioate

Octadecanedioic acid (ODDA, 5.00 g) was added to a 100-mL three-neckedround-bottom flask. A Dean-Stark condenser was attached, followed by theaddition of toluene to the ODDA and to the trap. 2-Methylpentyl alcohol(5.90 mL) was added to the ODDA mixture. The flask was immediatelypurged with nitrogen gas and p-toluenesulfonic acid (0.17 g) was added.The reaction mixture was heated to 115° C. and the reaction proceededfor 5 hours. Heat was then removed and the reaction mixture was allowedto cool to 60° C., at which point aqueous NaHCO₃ (saturated) was addedto achieve a neutral pH. After vigorous stirring, the organic layer wasseparated and dried over Na₂SO₄. The dried product was then subjected toa vacuum treatment to remove any residual solvent. A yellow oil wasobtained. Analysis by ¹H NMR provided the following chemical shifts:(400 MHz, CDCl₃) δ 0.90-0.85 (m), 1.10-1.20 (m), 1.21-1.50 (m), 1.55-1.7(t), 1.77 (o), 2.30 (t), 3.85 (dd), 3.95 (dd). Anaylsis by ¹³C NMRprovided the following chemical shifts: (400 MHz, CDCl₃) δ C, 173.947;CH, 32.366; CH₂, 69.200, 35.691, 34.438, 29.701, 29.684, 29.641, 29.516,29.319, 29.220, 25.095, 19.975; CH₃, 16.885, 14.258.

Prior to film preparation, the bis(2-methylpentyl) octadecanedioate(5.48 g) was purified using basic alumina (3.59 g). The basic aluminawas added to a 0.5-inch column, and the bis(2-methylpentyl)octadecanedioate was added atop the alumina and allowed to pass throughthe alumina. Nitrogen pressure was added to assist in the speed ofpurification. The purified plasticizer was incorporated in PVB films,below.

Polyvinyl butyral (PVB) films were prepared using varying amounts ofpurified bis(2-methylpentyl) octadecanedioate ranging from none to 30percent by weight of the plasticizer, relative to the total weight ofthe polymer composition. Table 2 shows the glass transition temperature(T_(g)) for films of varying amount of plasticizer incorporation.

TABLE 2 Plasticizer Loading (wt %) T_(g) (° C.) 0 76.0 10 61.7 20 51.430 51.8

Example 3 Bis(tri(ethylene glycol)monomethyl ether) Octadecanedioate

Dimethyl 1,18-octadecanedioate (ODDAME, 20.00 g), triethylene glycolmonomethyl ether (23.97 g), and a stir bar were added to an oven dried,250-mL three-necked round-bottom flask. A reflux condenser was placed inthe middle neck, a septum was placed in the right-hand neck, and a glassstopper was placed in the left-hand neck. The reflux condenser was inline with a chilled collection flask for excess methanol, and this wasin line with a water bubbler. A thermocouple and N₂ needle wereinserted, and a light N₂ flow was maintained over the course of thereaction. Tin(II) 2-ethylhexanoate was added under a positive N₂ flow,the system was inerted, and the temperature was raised to 160° C. Thereaction proceeded for over 4 hours, at which point the reaction wasremoved from heat, and a nitrogen sparge occurred over 1 hour. Thematerial was allowed to cool to 40° C. prior to removal from apparatus;the product was stored under nitrogen. A light beige solid wasrecovered. The product was analyzed by ¹H and ¹³C NMR. Analysis by ¹HNMR provided the following chemical shifts: (400 MHz, CDCl₃) δ 0.85-0.92(m), 1.20-1.40 (d), 1.57-1.68 (m), 2.34-2.28 (m), 3.37-3.45 (m),3.54-3.57 (m), 3.60-3.79 (m), 4.19-4.25 (m). Analysis by ¹³C NMRprovided the following chemical shifts: (400 MHz, CDCl₃) δ C, 173.619;CH, 34.049; CH₂, 71.800, 70.478, 70.438, 69.058, 63.202, 58.877, 29.527,29.510, 29.469, 29.330, 29.139, 28.994; CH₃, 24.773.

Prior to film preparation, the bis(triethylene glycol monomethyl ether)octadecanedioate was purified using basic alumina. The basic alumina wasadded to a 0.5-inch column, and the bis(triethylene glycol monomethylether) octadecanedioate was added atop the alumina and allowed to passthrough the alumina. Nitrogen pressure was added to assist in the speedof purification. The purified plasticizer was incorporated in PVB films,below.

Polyvinyl butyral (PVB) films were prepared using varying amounts ofpurified bis(triethylene glycol monomethyl ether) octadecanedioateranging from none to 30 percent by weight of the plasticizer, relativeto the total weight of the polymer composition. Table 3 shows the glasstransition temperature (T_(g)) for films of varying amount ofplasticizer incorporation.

TABLE 3 Plasticizer Loading (wt %) T_(g) (° C.) 0 76.0 10 55.4 20 42.230 30.5

Example 4 Bis(poly(ethylene glycol)monomethyl ether) Octadecanedioate

Dimethyl 1,18-octadecanedioate (ODDAME, 25.00 g), poly(ethylene glycol)methyl ether (avg. M_(n)=550, 100 g), and a stir bar were added to a250-mL three-necked round-bottom flask. A chilled distillation head (5°C.) was attached, in line with primary and secondary collection flasks,out to a bubbler. The collection flasks were both on dry ice, and thesystem was inerted via a slow N₂ sparge. The temperature was raised to55° C. with stirring, and the tin(II) 2-ethylhexanoate (0.58 g) wasadded. The temperature was raised to 140° C. and allowed to react for1.25 hours. The temperature was then raised to 130° C. and allowed toreact for 4 hours. The temperature was then raised once more, to 150° C.This was allowed to react for 1 hour at which point the heat wasremoved, and the product was allowed to cool with stirring. The productwas stored overnight, under N₂. The reaction was resumed under the sameconditions: 150° C., stirring, light nitrogen flow. The temperature wasincreased to 155° C., and the reaction was run another 6 hours. Theproduct was cooled, and again stored under nitrogen. Tin(II)2-ethylhexanoate (0.5578 g) was added to the reaction, and the reactionwas resumed and run for another 6 hours. The product was cooled, andagain stored under nitrogen. The reaction was resumed and tin(II)2-ethylhexanoate (0.8560 g) was again added. The reaction ran at 160° C.for another 5 hours. The reaction mixture was then dosed with tin(II)2-ethylhexanote (0.8578 g) and allowed to react at 165° C. for another 7hours. The product was cooled with stirring, transferred to vials forstorage, and stored under nitrogen. The product was analyzed by ¹H and¹³C NMR. Analysis by ¹H NMR provided the following chemical shifts: (400MHz, CDCl₃) δ 0.88-0.91 (m), 1.20-1.35 (d), 1.57-1.68 (m), 2.17 (s),2.30-2.34 (td), 3.38 (s), 3.54-3.56 (m), 3.56-3.74 (m), 4.21-4.23 (t).Analysis by ¹³C NMR provided the following chemical shifts: (400 MHz,CDCl₃) δ C, 173.629; CH, 34.031; CH₂, 77.489, 77.169, 76.849, 72.401,71.774, 70.422, 70.361, 70.201, 69.037, 63.194, 58.882, 29.514, 29.497,29.454, 29.316, 29.1330, 28.975; CH₃, 24.749.

Prior to film preparation, the bis(poly(ethylene glycol)monomethylether) octadecanedioate was purified using basic alumina. The basicalumina was added to a 0.5-inch column, and the bis(poly(ethyleneglycol)monomethyl ether) octadecanedioate was added atop the alumina andallowed to pass through the alumina. Nitrogen pressure was added toassist in the speed of purification. The purified plasticizer wasincorporated in PVB films, below.

Polyvinyl butyral (PVB) films were prepared using varying amounts ofpurified bis(poly(ethylene glycol)monomethyl ether) octadecanedioateranging from none to 40 percent by weight of the plasticizer, relativeto the total weight of the polymer composition. Table 4 shows the glasstransition temperature (T_(g)) for films of varying amount ofplasticizer incorporation.

TABLE 4 Plasticizer Loading (wt %) T_(g) (° C.) 0 76.0 10 55.1 20 40.430 29.6 40 p.s. *p.s. = phase separation

What is claimed is:
 1. A compound of formula (I):

wherein: X¹ is —(CH₂)₁₆—; R¹ is 2-methylpentyl, 2-ethylhexyl,2-butyloctyl, or 3-methylbutyl; R² is a branched or unbranched C₄₋₂₄alkyl, a branched or unbranched C₄₋₂₄ alkenyl, a branched or unbranchedC₄₋₃₀ oxyalkyl, or a branched or unbranched C₄₋₃₀ oxyalkenyl, each ofwhich is optionally substituted by one or more substituents selectedindependently from R³; R³ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆heteroalkyl, C₂₋₆ alkenyl, or C₂₋₆ heteroalkenyl.
 2. The compound ofclaim 1, wherein R² is a branched C₄₋₂₀ alkyl, a branched C₄₋₂₀ alkenyl,a branched C₄₋₂₀ oxyalkyl, or a branched C₄₋₂₀ oxyalkenyl, each of whichis optionally substituted by one or more substituents selectedindependently from R³.
 3. The compound of claim 2, wherein R² is abranched C₄₋₂₀ alkyl, which comprises branching at the 1-position of thealkyl moiety.
 4. The compound of claim 2, wherein R² is a branched C₄₋₂₀alkyl, which comprises branching at the 2-position of the alkyl moiety.5. The compound of claim 2, wherein R² is a branched C₄₋₂₀ alkyl, whichcomprises branching at the 3-position of the alkyl moiety.
 6. Thecompound of claim 2, wherein R² is 2-methylpentyl, 2-ethylhexyl,2-butyloctyl, or 3-methylbutyl.
 7. The compound of claim 1, wherein R²is branched or unbranched C₄₋₃₀ oxyalkyl, which is optionallysubstituted by one or more substituents selected independently from R³.8. The compound of claim 7, wherein R² is —(CH₂—CH₂—O)₁₋₁₂—(C₁₋₆unbranched alkyl).
 9. The plasticizer composition of claim 8, wherein R²is —CH₂—CH₂—O—CH₃, —(CH₂—CH₂—O)₂—CH₃, —(CH₂—CH₂—O)₃—CH₃,—(CH₂—CH₂—O)₄—CH₃, —(CH₂—CH₂—O)₅—CH₃, —(CH₂—CH₂—O)₆—CH₃,—(CH₂—CH₂—O)₇—CH₃, —(CH₂—CH₂—O)₈—CH₃, —(CH₂—CH₂—O)₉—CH₃,—(CH₂—CH₂—O)₁₀—CH₃, —(CH₂—CH₂—O)₁₁—CH₃, or —(CH₂—CH₂—O)₁₂—CH₂—CH₃.
 10. Aplasticizer composition, comprising a compound of claim 1.